Reactions of 1,4,7-trithiacyclononane, [9]aneS3, with early transition metal halides: synthesis and X-ray structure of {Fe([9]aneS3)2}[Sb2Cl8]

The reactions of titanium(III) and (IV) chlorides with the crown thioether [9]aneS3were investigated. [TiCl3-(MeCN)3] gives a purple 1:1 adduct with a proposed octahedral structure involving tridentate fac-attachment of the ligand. With [TiCl4(MeCN)2] the identity of the yellow 1∶1 adduct obtained is discussed in terms of a six-coordinate species with bidentate ligand chelation. The title compound was isolated from the reactions of [9]aneS3with [TiCl3(MeCN)3] [SbCl6] (by accident) and iron filings/SbCl5in MeCN solution and characterised crystallographically. The cation has two macrocyclic ligands coordinated facially to a six-coordinate Fe2+ion; the anion comprises dimeric [(SbCl4)2] units linked together into a polymeric chain by weak halogen bridging.